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United States Patent (19) 11 4,213,943

Martin 45 Jul. 22, 1980


54 PRODUCTION OF ALUMNUM CHLORIDE 4,096,234 6/1978 Martin et al. ........................ 423/36
FROM CLAY USING STAGED REACTORS Primary Examiner-Herbert T. Carter
(75 Inventor: Edward S. Martin, Lower Burrell, Attorney, Agent, or Firm-David W. Brownlee
Pa.
57 ABSTRACT
73) Assignee: Aluminum Company of America, Aluminum chloride is produced from clay containing
Pittsburgh, Pa. aluminum oxide and silicon oxide by chlorinating clay
21 Appl. No.: 972,468 in at least two stages with a mixture consisting of a
22 Filed: Dec. 22, 1978 chlorinating agent, a reducing agent, an alkali metal
compound catalyst and silicon tetrachloride in which
51 Int. C.’............................ C01F 7/56; C01F 7/58 the proportions and amounts of the feed gases to each
(52) U.S. C. .................................... 423/135; 423/136; stage are separately regulated to suit the needs of the
423/137; 423/343; 7.5/113 aluminum chloride production reaction in that stage.
58 Field of Search ............... 423/135, 136, 37, 341, The effluent gases from the successive stages are col
423/343, 495; 7.5/112, 113 lected and the silicon tetrachloride is separated from
56) References Cited such gases and recycled back into the reactors to pro
U.S. PATENT DOCUMENTS mote chlorination of the aluminum oxide in the clay
while suppressing net chlorination of the silicon oxide
1,866,731 7/1932 Slaib ..................................... 423/36 fraction of the clay.
1,875,105 8/1932 Muggleton et al. .. - 423/136
3,760,066 9/1973 Calcagno et al. . --- - - - - 423/136

4,086,320 4/1978 Martin et al. ........................ 423/136 8 Claims, 2 Drawing Figures


U.S. Patent Jul. 22, 1980 4,213,943

36

DEHYDRATED O
CAY
(IN)
34

4O
SPENT
(OUT)
CLAY

24
4,213,943 2
1
1973), page 20-64. As disclosed in such Handbook, the
PRODUCTION OF ALUMNUM CHILORDE two basic types of staging are vertical and horizontal.
FROM CLAY USING STAGED REACTORS Vertically staged reactors involve countercurrent
flow of gases and solids, which can be troublesome,
BACKGROUND OF THE INVENTION 5 especially when operated at elevated temperatures to
This invention relates to the production of aluminum process corrosive materials. For example, vertically
chloride from clay. More particularly, this invention staged reactors sometimes suffer from corrosion of the
relates to an improved system for chlorination of clays grids between stages, plugging of the grids, pressure
in multiple stages in which the proportions and amounts drops between stages, gas leaks, and material handling
of the chlorinating agent, reducing agent, alkali metal O problems. On the other hand, conventional horizontally
compound catalyst and silicon tetrachloride can be staged reactors typically feed the same gas through all
separately regulated to each stage to suit the needs of the stages and therefore aren't amenable to regulation of
the aluminum chloride production reaction in each gas flow into the various stages for most efficient opera
Stage. tion.
5
U.S. Pat. Nos. 4,086,320 and 4,096,234 describe the SUMMARY OF THE INVENTION
production of aluminum chloride by chlorination of
clay containing aluminum oxide and silicon oxide. The This invention provides a method and apparatus for
reducing agent in such chlorination is a gaseous agent producing aluminum chloride from clay in which the
such as carbon monoxide gas or phosgene (COC12), 20 clay is chlorinated in at least two stages by contacting
which can be used as both the reducing agent and the the clay successively with gaseous mixtures comprising
chlorinating agent. Chlorine gas can also be used as a a chlorinating agent and silicon tetrachloride in which
chlorinating agent if carbon monoxide is used as the the mixture of the gases is separately controlled for each
reducing agent. U.S. Pat. No. 4,096,234 further dis stage to suit the needs of the aluminum chloride produc
closes the addition of a catalyst such as potassium alumi 25 tion in that stage. Silicon tetrachloride is separated from
num chloride (KACl4) and recycling silicon tetrachlo the effluent gases produced by the reactor and is recy
ride back to the reaction zone to enhance the yield of cled back to the reaction stages in the proper propor
aluminum chloride from the aluminum oxide present in tions. The proportions of aluminum chloride and silicon
clay while reducing the amount of silicon tetrachloride tetrachloride in the effluent gases produced in each
produced in the chlorination reaction. U.S. Pat. No. stage may be measured to determine appropriate adjust
4,086,320 discloses that the clay should preferably be 30 ment for the concentration of silicon tetrachloride
comminuted to a particle size range of 90% by weight needed in the feed gas to avoid or minimize chlorination
smaller than 0.6 millimeter to provide maximum recov of the silicon oxide in each such stage.
ery of aluminum chloride from the clay. An object of this invention is to provide a method and
It is also known to use solid reducing agents in the apparatus for chlorinating clay which permits the clay
chlorination of aluminous materials to form aluminum 35
chloride. For example, U.S. Pat. No. 3,760,066 to Cal to be continuously fed through the apparatus and chlo
cagno et al teaches the production of aluminum trichlo rinated at a maximum production rate with a minimum
ride by reacting alumina particles with chlorine gas in a of capital expenditure.
fluidized bed containing alumina and carbon particles, A further object of this invention is to provide a
preferably coke, at 800-1000 C. system which permits adjustment of the gaseous mix
Raw materials useful in the chlorination process are ture used in chlorination to provide maximum effi
those containing an aluminum compound particularly ciency. As the alumina content in the clay is depleted as
where the major impurity is a silicon compound. Kaolin the clay moves from stage to stage, the ratio of silicon
clays (such as kaolinite) are particularly well suited for tetrachloride to the chlorinating agent can be separately
the chlorination process. 45 adjusted for each stage to optimum conditions of chlori
It is desirable to operate a reactor for chlorination of nating in each stage.
clay on a continuous basis with a continuous flow of The above and other objects and advantages of this
Solid reactants through the reactor and a continuous invention will be more fully understood and appreci
flow of gaseous aluminum chloride from the reactor. ated with reference to the following description and the
This means that solid clay particles must be continu 50 drawings attached hereto.
ously fed to and discharged from the reactor and that BRIEF DESCRIPTION OF THE DRAWINGS
the reaction bed consist of clay particles in various
stages of aluminum depletion. The degree of aluminum FIG. 1 is a cross-sectional view through a chlorina
depletion will depend on the kinetics of the reaction tion reactor having multiple horizontal stages in it with
involved and on the residence time of the clay in the 55 a separate gas distribution chamber for each stage to
reaction zone. permit independent control of the gaseous mixture fed
Operation of a single stage reactor with a continuous into each stage.
flow of clay through it will result in discharge of a FIG. 2 is a flow diagram of an alternative embodi
considerable amount of unreacted alumina unless the ment of this invention in which a separate container or
feed and discharge rates are quite low. However, low 60 reactor is provided for each stage of the process and the
feed and discharge rates result in a low rate of conver proportions of feed gases can be independently regu
sion of the aluminous material into aluminum chloride. lated for each reactor.
The conflict between high production rates and good DESCRIPTION OF PREFERRED
total extraction can be overcome by a process known as EMBODIMENTS
staging in which the solids are caused to follow a circu 65
itous path through the reactor. Staging can be accom In accordance with this invention, a staged reactor or
plished in a variety of ways as disclosed in the Chemical reactors are employed to chlorinate aluminous material
Engineer's Handbook by Perry and Chilton (5th Ed. such as kaolin clay to produce aluminum chloride. In
2
4,213,943
4.
the preferred embodiments of the invention, the param baffle plates 40 in each section to force the clay to fol
eters disclosed in U.S. Pat. Nos. 4,086,320 and 4,096,234 low a circuitous path through the reactor.
are used. That is, an aluminous material source such as In accordance with this invention, each plenum
kaolin clay is used having a surface area preferably of at chamber 18, 20, 22 has its own gas inlet 28, 30, 32 so the
least 15 m2/g and having a particle size (after drying proportions of the gases fed into such chamber can be
and comminution) of 90% by weight less than 0.6 milli individually controlled. This permits adjusting the rela
meter in diameter. The particles of aluminous material tive proportions of silicon tetrachloride and chlorine
are chlorinated in a fluidizing bed using a reducing fed to each stage of the reactor and also allows for the
agent such as carbon monoxide and a chlorinating agent use of different chlorine feed rates (or equivalently, gas
such as Cl2 or COCl2. In the case of phosgene (COCl2), 10 velocities) to be used in each stage of the reactor as a
the reducing and chlorinating agents are combined. The means of adjusting the gas-solid contact time according
clay is chlorinated in the presence of a catalyst which is to the reactivity of the solids in that stage.
an alkali metal compound. Preferred are alkali alumi The utility of being able to vary the ratio of chlorine
num halides and most particularly preferred is potas to silicon tetrachloride fed to each reactor stage arises
sium aluminum chloride (KAlCl4) or sodium aluminum 15 from the fact that the proportions of aluminum chloride
chloride (NaAlCl4). Other possible alkali aluminum and silicon tetrachloride produced vary with the extent
halides include rubidium aluminum chloride and lithium of the chlorination process (for either solid carbon or
aluminum chloride. These catalysts may be formed in carbon monoxide as the reducing agent). For example,
situ in the reactor by the addition to the reactor of an it has been found that the proportions of aluminum
alkali metal halide such as, for example, sodium chlo 20 chloride and silicon tetrachloride produced during
ride, sodium bromide, potassium iodide, or the like. chlorination of clay varies substantially as the alumina
The reducing agent in the reaction may be gaseous in content is depleted from the clay. The mole ratio of
the form of carbon monoxide or phosgene (COCl2), or aluminum chloride to silicon tetrachloride in the efflu
may be a solid reducing agent such as petroleum coke. ent gas decreases rapidly as the process reaches its con
An appropriate petroleum coke may be prepared by 25 clusion. It may therefore be desirable to provide a
making use of the delayed coking process. The green higher concentration of silicon tetrachloride as chlori
coke coming from the delayed coking process is cal nation nears completion to avoid net silicon chlorina
cined to remove moisture and volatiles. The resulting tion.
calcined coke is appropriate for use in the present inven Comparison of the concentrations of silicon tetra
tion. The amount of coke used for chlorination of alumi 30 chloride fed to the reactor using silicon tetrachloride
nous material such as kaolin clay may be 18% or more recycle (at constant silicon tetrachloride feed rates)
of the weight of the roasted clay, with 11.4-16% by with the silicon tetrachloride concentration in the efflu
weight preferred. ent gas from the reactor confirms the variation in the
The chlorination reaction is carried out at a tempera concentration of silicon chloride needed to avoid silicon
ture of from about 550-650 C. and may involve a resi 35 chlorination at each stage of the reaction. In the early
dence time of about 1 to 2 hours for the clay to pass stages of a chlorination reaction, the silicon tetrachlo
through all stages of the reactor at one atmosphere of ride concentration in the feed gas is more than the con
pressure, with more or less residence time required for centration in the effluent gas indicating reaction of sili
other pressure levels. Following chlorination, the alu contetrachloride with alumina to make aluminum chlo
minum chloride is separated from the effluent gases by ride. Late in the run, the situation is reversed. Thus, a
well-known techniques such as fractional distillation. higher ratio of silicon tetrachloride to chlorine may be
FIG. 1 illustrates a horizontally staged reactor 10 desirable in the later stages of the reaction process to
constructed in accordance with this invention having avoid net chlorination of silicon.
three fluidized bed sections 12, 4, 6 and three gas Another approach to avoiding net silicon tetrachlo
distribution plenum chambers i8, 20, 22 with a gas per 45 ride production from the overall reactor system would
meable plate 23 between the fluidized bed sections and be to feed relatively greater amounts of silicon tetra
the plenum chambers. The plenum chambers 18, 20, 22 chloride early in the reaction in order to convert it to
are separated by gas impermeable walls 25. The number aluminum chloride. The present invention makes it
of bed sections and gas distribution chambers may vary possible to operate the chlorination process at maximum
depending on the reactor design, reactant materials and 50 efficiency by independently adjusting the proportions
desired results. The reactor 10 comprises a metal shell of chlorine and silicon tetrachloride in the various
24 appropriately insulated to minimize heat loss and stages of the reaction process.
lined with materials which are resistant to attack by To illustrate the advantage of horizontally staging a
gaseous chlorine and the other reactants. The reactor reactor or reactors in accordance with this invention,
has an inlet 26 for dehydrated clay and possibly a solid 55 kaolin clay was chlorinated and the mole ratio of AlCl3
reducing agent if desired, inlets 28, 30, 32 for the gase to SiCl4 was measured as a function of chlorination
ous chlorinating and reducing agents, an outlet 34 for time. In the chlorination process, 0.75 mole of COCl2
the spent ciay, and an outlet 36 for effluent gases. The per hour was used as the chlorinating and reducing
fluidized bed sections 12, 14, 16 in the reactor are sepa agent for an agglomerate of kaolin clay and 5% KAlCl4
rated by vertical divider plates 38 and preferably have 60 at 600° C. and produced the following result:

MOLE RATIO AlCl3/SiCIA FOR CLAY AGGLOMERATES


Mole Ratio AlCl3/SiCl4 vs. Chlorination Time (Min)
Clay Agglomerate
Sample Roast Size Range
No. Conditions (mm) 15 30 45 60 75 90 105 120
1. 30 min at 0.595/ 5.8 5.7 2.0 .1 0.9 1.4 12.1 5.1
4,213,943
5
-continued
MOLERATO AlCl3/SiCl4 FOR CLAY AGGLOMERATES
Mole Ratio AlCl3/SiCl4 vs. Chlorination Time (Min)
Clay Agglomerate
Sample Roast Size Range -
No. Conditions (mm) 15 . . . .30. 45 60 75 90 105 120
700 C. 0.297 .. ..
2. 30 in at 0,595/ 5.7 12.3 12.8 14.2 10.6 5. 0.4 0.5
800 C. 0.297
3. 30 min at 0.595/ 5.5 3.6 m 2.2 2.0 0.5 - 0.6
850 C. 0.297
4. 5 min at 0.595/ 40.2 54.4 17.3 0.6 8.0 - 0.0 0.0
850 C. 0.297.
5. 15 min at 0.595/ - - 1.3 33.0 19.3 3.6 - 1.5 1.2
900 C. 0.297
6. 30 min at 0.595/ 3.8 4.6 7. 5.2 1.5 1.5 1.0 1.8
900 C. 0.297 - -
7. 30 min at 0.595/ 1.4 1.4 1.1 1.3 .5 0.9 1.0 1.1
950 C. 0.297
8. 30 min at . 0.595/ 1.7 1.7 2.0 3. 1.5 1.4 .2 1.1
1000 C. 0.297
9. 30 min at 4.8/3.4 .7 1.2 1.5 .9 1. 2.0 1.5 5
800 C.
0. 30 min at 2.4/1.7 1.4 3.4 2.8 1.9 1.2 14 1.4 1.2
800° C. -
1. 30 min at 0.6/0.3 5.7 12.3 12.8 14.2 10.6 5. 0.4 0.5
800 C.
12, 30 min at 0.3/0.2 26.6 18.9 19.0 0.3 2.4 1.8 1.5
800 C.
3. 30 min at 0.5/0.0 2.5 12.6 9.8 8.2 3.5 20 1.5 1.6
800 C.

Samples Nos. 2, 4, 11, 12 and 13 produced the best


results due to selection of proper parameters for roast- 30 invention are therefore not exposed to hot gases with
ing of the clay and agglomerate size. Those samples solid particles entrained therein so as to corrode and
show that the production of AlCl3 is substantially inde plug the grids.
pendent of aluminum depletion in the clay until near the FIG. 2 shows another embodiment of this invention
end of the chlorination process when the clay is nearly in which a plurality of separate reactor containers A, B,
depleted of aluminum. Consequently, it is not necessary 35 C and D are employed. In this embodiment, each reac
or desirable to provide countercurrent flow of clay and tor may have its own heat source such as a resistance
gases through a reactor with the fresh clay contacted by heater for heating the reactants to the desired tempera
substantially spent gas and the almost depleted clay ture. They may also include cooling equipment for
contacted by the richest gas as in a vertically staged removal of the exothermic heat of reaction from the
reactor. Instead, it is desirable to provide horizontal 40 gases as they are about to or have just emerged from
stages in accordance with this invention in which the reactors. Clay and petroleum coke are preferably pre
gas mixtures and residence times of the clay can be heated and fed into reactor A and then fed successively
controlled and adjusted depending on the specifics of to reactors B, C and D for complete chlorination of the
the reaction in each stage. For example, the use of a clay. The effluent gases from the reactors are collected
plurality of horizontal stages will help ensure that the 45 and aluminum chloride and silicon tetrachloride sepa
particles of clay will have more equal residence times in rated from such gases. Phosgene may also be recovered
the reaction in process. Some particles will sometimes from the effluent gases. All of the silicon tetrachloride is
move through one stage much more quickly than other preferably recycled into the reactors and chlorine
particles, but the residence times for the particles will added to it to chlorinate the clay. Carbon monoxide can
average out fairly equally when two or more stages are 50 also be added to the feed gases to supplement the coke
used. The employment of several horizontal stages hav as a reducing agent. Since the reactors each have their
ing separate gas plenums also provides the desired flexi own gas inlets, the proportions of gases fed to each
bility for fine tuning of the system for highest efficiency. reactor can be separately and independently varied
It is therefore seen that horizontally staged reactors of without regard for what happened in the previous stage
this invention are particularly well suited for chlorina 55 of the reaction process to maximize efficiency and re
tion of clay because such reactors permit adjustment of covery of aluminum chloride from the overall process.
the proportions of chlorinating agent from stage to This embodiment also makes it possible to separately
stage as chlorination progresses toward completion. measure the proportions of aluminum chloride and sili
Horizontally staged reactors of this invention also con tetrachloride in the effluent gases from each reac
avoid the problems inherent in countercurrent flow of 60 tor. This permits analysis of the reaction in each reactor
hot gases and solids through vertically stacked or and adjustment of the process for optimum efficiency.
staged reactors. In vertically staged reactors fluidizing It is therefore seen that an improved method and
grids which separate the stages may be corroded by the reactor or reactors are provided which permit adjust
hot gases and may also become plugged by the solids ment of the chlorination process for maximum effi
entrained in such gases. In contrast, a horizontally 65 ciency and maximum recovery of aluminum chloride.
staged reactor of this invention is not plagued by such Two embodiments of the invention have been selected
problems because the gases do not flow from stage to for purposes of illustration and explanation, but it will
stage through the reactor. The grids in a reactor of this be appreciated by those skilled in the art that numerous
4,213,943
7
modifications may be made in such embodiments with chloride and chlorinating agent in each feed to
out departing from the scope of the invention. maximize production of aluminum chloride and
What is claimed is: minimize chlorination of silicon in the clay.
1. A process for producing aluminum chloride from 2. A process as set forth in claim 1 in which the reduc
clay containing aluminum and silicon by chlorinating ing agent is solid carbon which is mixed with the clay
the clay at a temperature of about 550-650 C. for a and transferred from stage to stage with the clay.
period of about 1 to 2 hours in the presence of an 3. A process as set forth in claim 1 in which the reduc
alkali metal compound as a catalyst, which comprises: ing agent is a gas and is mixed with the gaseous chlori
contacting the clay with a reducing agent and a gase nating agent and silicon tetrachloride which is fed into
ous chlorinating agent in a first stage to chlorinate 10 each stage.
a part of the aluminum in the clay, 4. A process as set forth in claim 1 in which the clay
transferring the clay from the first stage to at least is fluidized in each stage of the reaction process by the
one additional stage and again contacting it with a gaseous agents flowing through the clay.
reducing agent and a gaseous chlorinating agent in 5. A process as set forth in claim 1 which includes
each such stage, 5 analyzing the effluent gases from each stage to deter
collecting the effluent gases from each stage and mine optimum proportions of the gases fed into each
separating aluminum chloride and silicon tetra stage.
chloride from such gases, 6. A process as set forth in claim 1 which includes at
recycling silicon tetrachloride which is separated least three stages.
from the effluent gases back into each stage for 20 7. A process as set forth in claim 1 in which petro
contacting the clay, and leum coke is used as a reducing agent.
providing separate feed of silicon tetrachloride and 8. A process as set forth in claim 1 which uses a sepa
chlorinating agent to each stage of the process and rate vessel for each stage. is is
regulating the relative proportions of silicon tetra
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45

50

55

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